Siloxy ketenes and products prepared therefrom

Abstract

A method of combining a siloxy group (--SiO--) with a ketene-reactive compound to form a siloxy-containing product comprises: (a) subjecting a silyl diketone to photolysis under conditions effective for generating a siloxy ketene intermediate therefrom, said silyl diketone having the formula ##STR1## wherein Si is silicon, R 1 and R 4 are hydrocarbon groups containing from 1 to 18 carbons, and R 2 and R 3 are hydrocarbon groups containing from 1 to 6 carbons, said photolysis being carried out by irradiating said silyl diketone with light of a wavelength from 200 to 800 nm; and, thereafter, (b) contacting the generated siloxy ketene intermediate with a ketene-reactive compound under conditions effective for reaction therewith, said compound being selected from the group consisting of (i) a diene polymer containing a plurality of unsaturated carbon bonds, (ii) an alkylene or cycloalkylene compound containing at least one unsaturated linkage; and (iii) an aldehyde containing one or more aldehyde groups.

I claim: 
     
       1. The siloxy-containing products produced by the method comprising the steps of: (a) subjecting a silyl diketone to photolysis under temperature conditions of from -20° to 50° C. effective for generating a siloxy ketene intermediate therefrom, said silyl diketone having the formula ##STR7##  wherein Si is silicon, R 1  and R 4  are hydrocarbon groups containing from 1 to 18 carbons, and R 2  and R 3  are hydrocarbon groups containing from 1 to 6 carbons, said photolysis being carried out by irradiating said silyl diketone with light of a wavelength from 200 to 800 nm; and thereafter,   (b) contacting the generated siloxy ketene intermediate with a ketene-reactive compound under temperature conditions of from about -20° to 50° C. effective for reaction therewith, said compound being selected from the group consisting of (i) a diene polymer containing a plurality of unsaturated carbon bonds, (ii) an alkylene or cycloalkylene compound containing at least one unsaturated linkage; and (iii) an aldehyde containing one or more aldehyde groups.   
     
     
       2. The siloxy-containing products produced by the method of claim 1 in which said ketene-reactive compound is diene polymer containing a plurality of unsaturated carbon bonds. 
     
     
       3. The siloxy-containing products produced by the method of claim 1 in which said ketone-reactive compound is alkylene or cycloalkylene compound containing at least one unsaturated linkage. 
     
     
       4. The siloxy-containing products produced by the method of claim 1 in which said ketene-reactive compound is an aldehyde containing one or more aldehyde groups. 
     
     
       5. The siloxy-containing polymer products produced by the method comprising the steps of: (a) subjecting a silyl diketone to photolysis under temperature conditions of from -20° to 50° C. effective for generating a siloxy ketene intermediate therefrom, said silyl diketone having the formula ##STR8##  wherein Si is silicon, R 1  and R 4  are hydrocarbon groups containing 1 to 6 carbons, and R 2  and R 3  are methyl groups, said photolysis being carried out by irradiating said silyl diketone with light of a wavelength from 200 to 800 nm; and   (b) concurrently with the generation of the siloxy ketene intermediate, contacting it with a conjugated diene polymer or copolymer containing a plurality of diene groups under temperature conditions of from -20° to 50° C. effective for reaction therewith.   
     
     
       6. The siloxy-containing products produced by the method comprising the steps of: (a) subjecting a silyl diketone to photolysis under temperature conditions of from -20° to 50° C. effective for generating a siloxy ketene intermediate therefrom, said silyl diketone having the formula ##STR9##  wherein Si is silicon, R 1  and R 4  are hydrogen groups containing from 1 to 18 carbons, and R 2  and R 3  are hydrocarbon groups containing from 1 to 6 carbons, said photolysis being carried out by irradiating said silyl diketone with light of a wavelength from 200 to 800 nm; and   (b) concurrently with the generation of the siloxy ketene intermediate contacting it with an alkylene compound under temperature conditions of from -20° to 50° C. effective for reaction therewith, said compound being selected from the group consisting of aliphatic alkenes containing from 2 to 20 carbons and cycloalkenes containing from 3 to 20 carbons.   
     
     
       7. The siloxy-containing products produced by the method comprising the steps of: (a) subjecting a silyl diketone to photolysis under temperature conditions of from -20° to 50° C. effective for generating a siloxy ketene intermediate therefrom, said silyl diketone having the formula ##STR10##  wherein Si is silicon, R 1  and R 4  are hydrogen groups containing from 1 to 18 carbons, and R 2  and R 3  are hydrocarbon groups containing from 1 to 6 carbons, said photolysis being carried out by irradiating said silyl diketone with light of a wavelength from 200 to 800 nm; and   (b) concurrently with the generation of the siloxy ketene intermediate contacting it with aldehyde compounds containing from 1 to 2 aldehyde groups and from 2 to 20 carbons under temperature conditions of from -20° to 50° C. effective for reaction therewith.   
     
     
       8. A conjugated diene polymer or copolymer containing a plurality of siloxy cyclobutanone groups represented by the formula ##STR11## wherein Si is silicon, R 1  and R 4  are hydrogen groups containing from 1 to 18 carbons, and R 2  and R 3  are hydrocarbon groups containing from 1 to 6 carbons. 
     
     
       9. A coated article comprising a substrate coated on at least one surface with a layer of the polymer or copolymer of claim 8. 
     
     
       10. A conjugated diene polymer or copolymer containing a plurality of siloxy cyclobutanone groups represented by the formula ##STR12## wherein Si is silicon, and R 1  and R 4  are hydrocarbon groups containing from 1 to 6 carbons. 
     
     
       11. A coated article comprising a substrate coated on at least one surface with a layer of the polymer or copolymer of claim 10.